Chemical Bonding:

Concept & Examples

Instructor
Major Kayesh Md. Ashraf, Dr. Engg.
MIST
 Kossel & Lewis Theory (Electronic Theory)
 Valence electrons are the electrons in the highest occupied energy level of an elements atoms.
They determine the chemical properties of an element.
 Chemical bonding may result from
transfer of one/more electrons (ionic bond),
sharing of electrons between atoms (covalent bond, coordination covalent bond).
 Electrons are transferred or shared until each atom acquires an OCTET of outer shell (valence)
electrons (OCTET RULE).

 Octet Rule – the tendency to achieve an electronic configuration with eight valence electrons. An octet of
electrons consists of a full s and p subshells of an atom.
 Lewis Structures – a combination of Lewis symbols representing the transfer or sharing of electrons in a
chemical bond.
 Lewis structures
 Lewis Structure: Representation of a molecule that shows how
the valence electrons are arranged among the atoms in the
molecule.

 Bonding involves the valence electrons of atoms.

Example: Na● H-H

 Dots around elemental symbol

Symbolize valence electrons
Thus, one must know valence electron configuration
Lewis electron-dot symbols for some elements
 Example

Write the Lewis Structure for the following molecules:

1) H2O
2) CCl4
3) PH3
4) H2Se
5) C2H6
6) CO2
7) C2H4
8) C2H2
9) SiO2
 Types of Chemical Bonding

 Ionic bonding involves the transfer of

electrons and is usually observed when a
metal bonds to a nonmetal.
 Covalent bonding involves the sharing of
electrons and is usually observed when a
nonmetal bonds to a nonmetal.
 Metallic bonding involves electron pooling
and occurs when a metal bonds to another
metal.
 Other types of bonding
Non polar

Polar
 Formation of ionic compound
Formed when one or more electrons are transferred from one atom to the other to complete the
orbital in each case. Usually we see this bond formation between metal and non-metal.
e
Metal atom Non-metal atom
donate electron receive electron

Achieve the stable

electron arrangement

donate electron accept electron

Cation Neutral Anion
(+) atom (-)
 Formation of NaCl ionic compound
 The electronic configuration of the resulting
atoms are identical to that of an atom of one
of the inert gases.
o +
Na Na
1s22s22p63s1 1s22s22p6
Neon structure
Na: 1s22s22p63s1 Cl: 1s22s22p63s23p5
×× ××
-
× Cl ×× ×
× Cl ××
×× ××

1s22s22p63s23p5 1s22s22p63s23p6
Argon structure
×× ××
-
o +
Na + × Cl ×× Na ×
× Cl ××
×× ××
Na+: 1s22s22p6 Cl-: 1s22s22p63s23p6
Neon structure Argon structure
 Home Work:

Which one more ionic in character?

1. MgCl2 & MgI2

1. BaCl2 & BeCl2

Is it the size and the extent of overlapping?

 Limitations of ionic bond

 Limitations to gain and lose electrons by an atom to form positive and

negative ions because of the energy consideration.
 Many cations do not have inert gas structure (not always ns2np2)

Cu+, Zn2+ have outer 3s23p63d10 groupings

Ag+ In3+ have outer 4s24p64d10 grouping

 Electron grouping s2p6d10 in Zn2+, Cd2+ and Hg2+ are stable and no extra
e- is lost from these cations.
 Transition metal cations show variable charge and do not have either
inert gas s2p6 or 18 electron s2p6d10

Fe: 1s22s22p63s23p63d64s2
Fe2+:1s22s22p63s23p63d6
Fe3+: 1s22s22p63s23p63d5
 Exceptions to Octet Rule

Odd-electron species

 NO
 NO2

Incomplete octet
BH3
 Expanded octet
Some central atoms can exceed an octet
Third period and higher elements can do this
E.g., Al, Si, P, S, Cl, As, Br, Xe, etc.
d-orbitals can accommodate extra electrons

 PCl5
 XeF2

Practice
 SCl6
 XeF4
 Properties of ionic compounds
Crystalline state
Composed of clusters of ions
Forms crystal lattice or atomic network
Produces geometric shapes b/c of the arrangement of the ions in space

Crystal pattern of NaCl

Packing of NaCl (FCC)
 Electrical Conductivity
 Conduct electricity in fused or liquid state or in
solutions.
 In solutions or in fused state, ions move freely under
the influence of E. field
 Isomorphism
(existence of two or more different substances in
the same crystal form and structure)

 Same electronic arrangements in the ions (different atoms in

different molecules)
 Show similar crystalline forms

Na+: 1s22s22p6 F-: 1s22s22p6

Mg2+: 1s22s22p6 O2-: 1s22s22p6
 Dielectric Constant
Polar molecule or dipole orient in an electrostatic field
Positive end of polar molecule is attracted to the negative pole and vice versa
Oriented dipole oppose the field and reduce the intensity of the E field
Ionic compounds have the highest D. Constant
 Melting and boiling point

 Polar molecule shows dipole association.

 Ions in a lattice are bound together by electrostatic force.
 A considerable amount of work is needed to separate
them from one another.
 They have high P & MP .
 Faster Reactivity
 Because ionic compounds exist as ion in aqueous solutions, therefore, no bond is to be broken, only
few bonds are formed.

Solubility
 Ionic compounds are more soluble in polar solvents than non-polar solvents
 Solvent dipoles orient themselves surrounding the ions (cations & anions).
 This renders the inter-ionic force weaker and pulls away some ions into the solution
 Formation of covalent compound
 Formed when a pair of electrons is shared by between atoms (same
or different) to form stable structures (octet structure).
 Compounds containing these bonds are called covalent compounds.
e 1e e
Atom # 1 1e Atom # 2
donate 1 electron donate 1 electron
Achieve octet
electron arrangement

e
+
e Ho + ×H
1 1 1s1 1s1
Single
covalent bond


H o× H or H - H

2 2
 oo x x oo x x
o x o
o Fo + x F x o F ox F x
x
oo x x oo x x

After sharing
1212s22p5 1212s22p6
Neon structure

xx xx
Ho + x Cl xx H x Cl xx
o
xx xx
1s1 1212s22p63s23p5

H H
xo xo
H
x x x
H o C o H x N o H x ox
x O o
ox xo x
x H
H H
xx
 Double covalent bond Triple covalent bond

O(8) O(8) N(7) N(7)

 Limitations of Covalent bond
(Lewis Concept)
 Covalent compounds are stable by attaining inert gas structure: no reason offered in this theory
 Pair of e- constitute a stable chemical structure: no reason offered in this theory
F
xo x
 Did not present real understanding of the nature of chemical bond B o F
xo
 Some compounds don’t have required number of eight electrons F
 Similarly, e- configs of PCl5, SF6 do not correspond with this theory.
They have more than 8e-.
 Lewis structure does no explain the magnetic properties of O2.

 There are many compounds where more than one Lewis structures
can be possible e.g., N2O, HN3, CO2 etc.: only one exists.
 Paramagnetism of Oxygen

O: 2s22s22p4 O: 2s22s22p4
O: 2s22s22px22py12pz1 O: 2s22s22px22py12pz1
Potential Energy Diagram of Covalent Bond
 Coordination covalent bond
 A coordinate bond (also called a dative covalent bond) is a covalent bond (a
shared pair of electrons) in which both shared electron pair come from one
atom.
 A coordinate covalent bond is usually shown with an arrow.

H F H F H F
ox oo ox oo ox oo
+ or
x x o x x o x o
H o N x B o F H o N x B o F H o N B o F
xo oo xo oo xo oo
H F H F H F
Donor atom Acceptor atom
N F
 Some donor atoms: F-, OH- etc.  How many bonds are there in these compounds?
 Acceptor atoms: H+, AlBr3 etc. 1. H2SO4
2. H3PO4
3. NH4Cl
4. POCl3
Valence bond theory
Valence bond theory
Valence bond theory
Valence bond theory
Valence bond theory
 Valence bond theory
Heitler-London Theory:

 An atom combines with another atom through the

pairing of electrons of opposed spins.

 N (1s22s22px12py12pz1) can pair with three F atom to

form NF3 not NF5 since no more orbitals are available
in n=2.

 P (1s22s22px12py12pz13d0) can pair with five F atom to

form PF5 since 3d orbital is available in n=3.
 Pauling-Slater Concept of VBT
 Two half-filled orbitals overlap to form a covalent bond. The electrons in this new probability density
are then shared by both atoms (equally attracted to both nuclei), arrange themselves to have
maximum overlap of their half filled orbitals, producing a bonding orbital of lowest energy
Other consideration
1. The orbitals must have similar energies
2. The orbitals must overlap to a
considerable extent
3. The orbitals must possess the same
symmetry about the molecular axis.
4. According to the Pauli exclusion
principle each bonding orbitals contains
two electrons of opposed spin
 s-orbital can combine with another s
or p or d orbital in the direction of the
bond
 px with px, however if two p orbitals
are involved, they combine sidewise
or laterally
 Symmetry
Are they symmetric?

Are we poly-symmetric?
 bond
 bond
 bond
 bond
 bond
 Example
H2 molecule
HCl molecule
N2 molecule
N2 molecule
 LIMITATIONS OF VALENCE BOND THEORY

Does not give quantitative interpretation of magnetic data.

Does not explain the color exhibited by coordination
compounds.
Does not give quantitative interpretation of thermodynamic
or kinetic stabilities of coordination compounds.
Does not make exact predictions regarding the tetrahedral
and square planar structures of coordinate compounds.
Does not distinguish between weak and strong ligands
 Molecular orbital theory (MOT)
 Each electron is placed in a molecular orbital which is polynuclear
 It is associated with all the atomic nuclei present in the molecule
 Electrons are placed in the available molecular orbitals one at a time
 The lowest energy molecular orbitals are being filled first.
 Each molecular orbitals can accommodate a maximum of two electrons
with opposite spin

Other consideration

1. The orbitals must have similar energies

2. The orbitals must overlap to a
considerable extent
3. The orbitals must possess the same
symmetry about the molecular axis.

Is it possible have He2?

 The mathematical treatment for the combination of atomic orbitals for obtaining the
molecular orbitals is known as linear combination of atomic orbitals (LCAO).
Suppose two atomic orbital wave functions of A & B are
A & B

combine to form two new molecular wave functions

𝜓+ = 𝐶𝐴 𝜓𝐴 + 𝐶𝐵 𝜓𝐵 𝜓+2 = 𝐶𝐴2 𝜓𝐴2 + 2𝐶𝐴 𝜓𝐴 𝐶𝐵 𝜓𝐵 + 𝐶𝐴2 𝜓𝐵2

𝜓− = 𝐶𝐴 𝜓𝐴 − 𝐶𝐵 𝜓𝐵 𝜓−2 = 𝐶𝐴2 𝜓𝐴2 − 2𝐶𝐴 𝜓𝐴 𝐶𝐵 𝜓𝐵 + 𝐶𝐴2 𝜓𝐵2

CA & CB are the mixing coefficients

For homonuclear diatomic molecule A = B (H2)

𝐶𝐴 = 𝐶𝐵 (mathematical details omitted)
𝐴 and 𝐵 are equal
𝐶𝐴2 = 𝐶𝐵2 = ½ for a homonuclear bond A B
𝐶𝐴2 = 𝐶𝐵2 = 1 for a heteronuclear bond (ionic)
A B
Covalent bond: bonding e- distributed equally
between A & B.
Ionic bond: these (e-) r in the valence level of atom
B to produce (-)ve charge atoms, having none of
the electron wave in the valence level of A
indicates the (+) ve charge ions (CB2=0).
The combination gives two molecular orbitals: one A+ B-
with lower energy the other with higher energy.
The energy of the molecular orbitals lower than A
B
the original one is known as the bonding molecular
orbital; the reverse is the antibonding orbital.
Bonding orbital electrons signify the attraction,
anti-bonding orbital electrons signify repulsion.
Electrons placed in the deep seated non-bonding
do not take part in bonding (non-bonding
electrons)
 CH4

Anti-bonding

Anti-bonding

Bonding

Bonding
The σ bond

Electron density is
between the nuclei of
the overlapping atoms
The π bond

Electron
densities are
above and below
the nuclei of the
bonding atoms
Only p orbitals
can form pi
bonds!
 Sigma and Pi Bonds

Single Bond = 1 sigma bond

Double Bond = 1 sigma bond and 1 pi bond
Triple Bond = 1 sigma bond and 2 pi bonds
 Double Bond
one π bond & one σ bond
 Triple bond
two π bond & one σ bond
The benzene ring
 Home Assignment
1. Write note on
1. Lanthanide contraction
2. Crystalline state
3. Aufbau principle
4. Isomorphism
5. Hund’s rule
6. (n+l) rule
2. MOT diagram of O2 and HCl
3. MOT diagram of F2 and HF
4. Shapes of the following by VSEPR
1. BF3, NH3, CH4 H2O & SO2
5. Draw diagram of Rutherford Bohr and Planck’s atomic model
6. Electronic structure of
Cr (24), Cu (29), Br (35), Rb (37) and Cl (17), Fe (25)
7. Which is more ionioc
1. MgCl2 & MgI2
2. BaCl2 & BeCl2
11. Draw the geometry of the following
PO42-, I3-, PF3 andCH3Cl
12. Benefits and limitations of MOT
 Polyatomic Ions
A polyatomic ion is a tightly bound group of atoms (usually different atoms) that
has a positive or negative charge and behave as a unit.
A group of atoms that are covalently bound and as a whole have a charge or a
charged particle consists of more than one atom..

Try these: NH4+

HSO4-
OH-
HPO42-
+
H3O+
 Hybrid bond
How can we explain bonds in the following compounds

BF3, CCl4, PCl5 PCl3 etc.

B: 1s22s22p1 (monovalent)
C:1s22s22p2 (divalent)

They use different hybrid bonds to make bond with other atoms

Hybridization
 hybridization) is the concept of mixing atomic orbitals into new hybrid
orbitals (with different energies, shapes, etc., than the component atomic
orbitals) suitable for the pairing of electrons to form chemical bonds
 Promotion & Hybridization

Certain atoms can change their electron configuration in

order to bond and form a wide variety of compounds

This “change” in electron configuration takes place in two

steps: Promotion of an electron to a higher energy orbital &
hybridization or blending of orbitals creating a new type of
orbital for bonding
 Promotion
Most of the time atoms exist in their “ground state” but, in certain cases the instant
before bonding promotion takes place allowing more bonding spaces:
 Hybridization
The merging of orbitals

p
s

p
s

 Merging orbitals must all be half filled

 No orbitals are “lost” due to merging – if you blend one s orbital and
one p orbital you will end up with two hybrid orbitals!
 Hybridization
Continued

 Mix at least 2 non-equivalent atomic orbitals (eg. s and p). Hybrid

orbitals have different shapes from original atomic orbitals
 Covalent bonds are formed by:
 Overlap of hybrid orbitals with atomic orbitals
 Overlap of hybrid orbitals with other hybrid orbitals
Example: Hybridization in carbon
to form methane (CH4)
 Types & Names of hybrid orbitals
• The type of hybrid orbital depends upon the orbitals which have been blended

109o
 sp2 Hybridization in BF3
_ _ _
↓ 2p1 Unhybridized Boron
2s2

For BF3, 3 hybrid orbitals are needed, so 3 atomic

orbitals are required as follows: (s + p + p) = sp2

_ _ _
sp2 sp2 sp2 Hybridized Boron
3 sp2 orbitals needed
to form 3 sigma bonds
sp Hybridization in BeCl2
_ _ _
↓ 2p Unhybridized Be
2s2
• For BeCl2, 2 hybrid orbitals are needed, so 2 atomic orbitals are
required as follows: (s + p ) = sp
_ _
sp sp Hybridized Be
Once hybridization has occurred – hybridized
orbitals are ready to bond – just like regular
orbitals

Bonding in hybridized orbitals

Because of their shape,
hybrid orbitals can only
undergo sigma bonding.
Shapes & Hybrids
 Hybridization Involving d Orbitals

promote

3s 3p 3d 3s 3p 3d
unhybridized P atom vacant d orbitals
P = [Ne]3s23p3 hybridize

Ba
F

F Be five sp3d orbitals 3d

P F Be

F
Be degenerate
F orbitals

Ba (all EQUAL)

Trigonal bipyramidal
 Resonance structures
When structures can be written in more than one way
O3
+

Actual molecule is “in-between”

Practice Resonance hybrid
NO2- Another example
NO3- HCO3-
What would its resonance hybrid look like?
H2O2
H3O+
 Electronegativity: The relative ability of an atom in a
molecule to attract shared electrons to itself.

Example: Fluorine has the highest electronegativity.

Similar electronegativities between elements give non-polar
covalent bonds (0.0-0.4)
Different electronegativities between elements give polar
covalent bonds (0.5-1.9)
If the difference between the electronegativities of two
elements is about 2.0 or greater, the bond is ionic
 Molecular structure CO2
BF3
Molecular Structure: or geometric structure refers to the three- CH4
dimensional arrangement of the atoms in a molecule.

Bond Angle: The angle formed between two bonds in a molecule.

SH6
PCl5
Bond Order
•The term bond order refers to the number of
bonds that exist between two atoms.
• The bond order of a diatomic molecule is
defined as one-half the difference between the
number of electrons in bonding orbitals, nb ,
and the number of electrons in antibonding
orbitals, na
.
𝒏𝒂nb−-n𝒏
a 𝒃
𝑩𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓:
𝟐
For better preparation, read by heart
 Answers of the Previous years questions (must)
 Books (S Haider)
 Slides (least priority)
 Molecular structure: VSEPR
The VSEPR Model: The valence shell electron pair repulsion model is useful for
predicting the molecular structures of molecules formed from nonmetals.

The structure around a given atom is determined by minimizing repulsions between

electron pairs.

The bonding and nonbonding electron pairs (lone pairs) around a given atom are
positioned as far apart as possible.
Lone pair-lone pair repulsion
bond pair-lone pair repulsion
bond pair- bond pair repulsion
Steps for Predicting Molecular Structure Using the VSEPR
Model
1. Draw the Lewis structure for the molecule.
2. Count the electron pairs and arrange them in the way
that minimizes repulsion (that is, put the lone pairs as
far apart as possible).
3. Determine the positions of the atoms from the way the
electron pairs are shared.
4. Determine the name of the molecular structure from the
positions of the atoms.
 Which compound contains both
ionic and covalent bonds?
1. HBr For better preparation, read by heart
 Answers of the Previous years questions (must)
2. CBr4  Books (S Haider)
 Slides (least priority)
3. NaBr
4. NaOH

Draw the electron dot structure for the polyatomic boron

tetrafluoride anion (BF4-)
 Other types of bond
1. Metallic bond
2. H2 bond
3. Van der Waal’s force
I. London force (non-polar) &
II. dipole-dipole interaction (polar)
van der Waal’s force
 Metallic Bonding
Metallic Bonding – “Delocalized sea of electrons
theory”

 The nuclei are arranged in a systematic lattice.

 The bond strength relies on the nuclear charge
and the number of valence e- Ex. Mg is stronger
than Na
 The valence electrons form a sea of free moving
electrons that are attracted to multiple positive
nuclei.

 Metallic Bonding Conducts

Electricity as a result of free
electrons. Malleability and
ductility results from the nuclei's
ability to move passed each other

 Metallic Bonding
 Remember: in ionic bonds some atoms want e- and some don’t in covalent bonds, all atoms share e- in
metals, no one atom wants the e-
 H2 bond
 a weak bond between two molecules resulting from an electrostatic attraction
between a proton in one molecule and an electronegative atom in the other.
 van der Waal’s force
 weak, short-range electrostatic attractive forces between uncharged molecules, arising from
the interaction of permanent or transient electric dipole moments.
 The magnitude of this force increases with increase in the number of electrons per molecule
 It causes the inert gases and the halogens to become liquid and solid when the temp is lowered
 London force
 The London dispersion force is the weakest intermolecular force.
 The London dispersion force is a temporary attractive force that results when the electrons in
two adjacent atoms occupy positions that make the atoms form temporary dipoles.
 This force is sometimes called an induced dipole-induced dipole attraction.

For better preparation, read by heart

 Answers of the Previous years questions (must)
 Books (S Haider)
 Slides (least priority)
Interaction

Bond strength
Formula weight, g/mol
Boiling point (oC)
End
 Valence bond and molecular orbital theories

 Valence bond and molecular orbital theories are used to explain chemical bonding.
 Two atoms that have unpaired electrons in their orbitals can overlap to give rise to
a chemical bond.
 A sigma bond (σ) forms when two atomic orbitals overlap between the nuclei of
two atoms (also known as the internuclear axis).
 Pi bonds (π) occur when two atomic orbitals overlap outside of the space between
the nuclei (outside of the internuclear axis).
 The strongest bonds form with maximum overlap between orbitals.
Ionic Compound: A compound resulting from a positive ion (usually a metal) combining
with a negative ion (usually a non-metal).
Example: M+ + X-  MX

Covalent Bond: Electrons are shared by nuclei.

Example: H-H
Polar Covalent Bond: Unequal sharing of electrons by nuclei.
Example: H-F
Hydrogen fluoride is an example of a molecule that has bond polarity.

Coordination covalent bond: Shared pair of electrons come from one atom shared by both
nuclei.
Example

Metallic bond
 Rules for Lewis structures of
molecules
1. Write out valence electrons for each atom Example
2. Connect lone electrons because lone electrons
are destabilizing H2
1. Become two shared electrons Duet rule
1. Called a “bond”
F2
3. Check to see if octet rule is satisfied Octet rule
1. Recall electron configuration resembling noble gas
1. In other words, there must be 8 electrons (bonded or O2
non-bonded) around atom N2
1. Non-bonded electron-pair
1. Called “lone pair”
Bond: Force that holds groups of two or more atoms together and makes the
atoms function as a unit.
Example: H-O-H

Bond Energy: Energy required to break a bond.

Symmetrical Unsymmetrical
distribution distribution
+ -

electrons

Nucleus
 Faster Reactivity
 because ionic compounds exist as ion in aqueous solutions, therefore,
no bond is to be broken, only few bonds are formed.

Solubility
 Ionic compounds are more soluble in polar solvents than non-polar solvents
 Solvent dipoles orient themselves surrounding the ions (cations & anions).
 This renders the inter-ionic force weaker and pulls away some ions into the solution

+ - + -
Solution
- + - +
Crystallization
+ - + -

- + - +